Synthesis · Cellulose Nanofiber @ Conductive Metal-Organic Frameworks for High-Performance Flexible Supercapacitors

12 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Complete recipeSource: Both

Route 1: Other

article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HHTP Nanofibers

Metal precursorsNi(OAc)2.4H2O (60 mg, 0.24 mmol)

Linker precursorsHHTP (42 mg, 0.12 mmol)

Solventswater

Additivesion-exchanged CNFs (20 mL, 5 mg mL^-1)

Temperature80

Time12

Substrate orientationc-MOF grown on ion-exchanged cellulose nanofiber surface

Work-upsuspension filtered on PVDF membrane; product washed with deionised water and acetone five times; dispersed in water

Scalability contextProduces aqueous CNF@Ni-HHTP nanofiber suspension that can be vacuum filtered into freestanding nanopaper.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	60 mg, 0.24 mmol · in 10 mL water	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HHTP Nanofibers
Linker	HHTP	42 mg, 0.12 mmol · in 10 mL water	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HHTP Nanofibers
Solvent	water	10 mL + 10 mL + CNF suspension water	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HHTP Nanofibers
Other	ion-exchanged CNFs	20 mL · 5 mg mL^-1	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HHTP Nanofibers
Solvent	acetone	washed five times	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HHTP Nanofibers

Complete recipeSource: Main

Route 2: Other

rendered page 7 / article p.9584 · Methods - Fabrication of CNF@c-MOF Nanopapers · Figure S2

Solventswater

AdditivesCNF@Ni-HHTP nanofiber aqueous suspension

Temperature70

Time12

Substrate orientationvacuum filtration onto membrane

Work-upVacuum filtered; mould pressed between two metal plates; dried at 70 degrees C for 12 h.

Activationdried at 70 degrees C for 12 h

Scalability contextFreestanding nanopaper formed from 3 mg mL^-1 aqueous nanofiber suspension.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	aqueous suspension of CNF@c-MOF nanofibers	3 mg mL^-1	rendered page 7 / article p.9584 · Methods - Fabrication of CNF@c-MOF Nanopapers · Figure S2

Complete recipeSource: Both

Route 3: Other

article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HITP Nanofibers

Metal precursorsNi(NO3)2.6H2O (66 mg, 0.23 mmol)

Linker precursorsHITP.6HCl (100 mg, 0.18 mmol)

Solventswater

Additivesion-exchanged CNFs (30 mL, 5 mg mL^-1); concentrated aqueous ammonia (3 mL, 14 mol L^-1)

Atmosphereair flow for 2 h, then without air flow for 4 h

Temperature70

Time6

Substrate orientationc-MOF grown on ion-exchanged cellulose nanofiber surface

Oxidant / reductantair flow may act as oxidative condition during first stage; not explicitly described as oxidant

Work-updark suspension centrifuged and washed with deionised water three times

Scalability contextProduces aqueous CNF@Ni-HITP nanofiber suspension that can be vacuum filtered into freestanding nanopaper.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	66 mg, 0.23 mmol · in 10 mL water	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HITP Nanofibers
Linker	HITP.6HCl	100 mg, 0.18 mmol · in 25 mL water	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HITP Nanofibers
Base	concentrated aqueous ammonia (NH4OH)	3 mL · 14 mol L^-1	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HITP Nanofibers
Other	ion-exchanged CNFs	30 mL · 5 mg mL^-1	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HITP Nanofibers
Solvent	water	10 mL + 25 mL + CNF suspension water	article p.9584 / rendered p007 · Methods - Synthesis of CNF@Ni-HITP Nanofibers

Complete recipeSource: Main

Route 4: Other

rendered page 7 / article p.9584 · Methods - Fabrication of CNF@c-MOF Nanopapers · Figure S2

Solventswater

AdditivesCNF@Ni-HITP nanofiber aqueous suspension

Temperature70

Time12

Substrate orientationvacuum filtration onto membrane

Work-upVacuum filtered; mould pressed between two metal plates; dried at 70 degrees C for 12 h.

Activationdried at 70 degrees C for 12 h

Scalability contextFreestanding nanopaper formed from 3 mg mL^-1 aqueous nanofiber suspension.

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	aqueous suspension of CNF@c-MOF nanofibers	3 mg mL^-1	rendered page 7 / article p.9584 · Methods - Fabrication of CNF@c-MOF Nanopapers · Figure S2

Complete recipeSource: Main

Route 5: Other

rendered page 7 / article p.9584 · Methods - Fabrication of Supercapacitors · Figure 4

Solventsdeionised water

AdditivesPVA; KCl; filter-paper separator; graphite-paper current collectors; two CNF@c-MOF nanopaper electrodes

Temperature90

Substrate orientationsandwich device stack

Work-upPVA/KCl gel prepared at 90 degrees C; electrodes immersed in gel for 30 min; separator sandwiched between two identical nanopaper electrodes; graphite paper used as current collectors.

Scalability contextFlexible symmetric supercapacitor assembled from two 1.5 cm x 2 cm x 0.005 cm nanopaper electrodes.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	poly(vinyl alcohol) (PVA)	1.0 g · in 10 mL deionised water with KCl	rendered page 7 / article p.9584 · Methods - Fabrication of Supercapacitors · Figure 4
Electrolyte	KCl	0.746 g · in 10 mL deionised water	rendered page 7 / article p.9584 · Methods - Fabrication of Supercapacitors · Figure 4
Solvent	deionized water	10 mL	rendered page 7 / article p.9584 · Methods - Fabrication of Supercapacitors · Figure 4
Other	CNF@c-MOF nanopaper electrodes	two pieces, 1.5 cm x 2 cm x 0.005 cm, 26.7 mg	rendered page 7 / article p.9584 · Methods - Fabrication of Supercapacitors · Figure 4
Other	filter paper separator	one piece	rendered page 7 / article p.9584 · Methods - Fabrication of Supercapacitors · Figure 4
Other	graphite paper current collectors	two pieces	rendered page 7 / article p.9584 · Methods - Fabrication of Supercapacitors · Figure 4

Complete recipeSource: SI

Route 6: Other

SI p.3 · Supplementary Experimental Section - Fabrication of CNF-c-MOFs paper

Metal precursorsNi-HHTP c-MOF powder (15 mg)

Solventsdeionised water (50 mL) plus CNF suspension water

AdditivesCNF suspension (17 mL, 5 mg mL^-1)

Atmosphereambient

Temperature70 drying

Time20 min sonication; 12 h drying

Substrate orientationdirect mixed CNF/c-MOF paper control

Work-upsonicated 20 min, vacuum filtered, mould pressed between two metal plates

Activationdried at 70 C for 12 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-HHTP c-MOF powder	15 mg	SI p.3 · Supplementary Experimental Section - Fabrication of CNF-c-MOFs paper
Other	CNFs suspension	17 mL · 5 mg mL^-1	SI p.3 · Supplementary Experimental Section - Fabrication of CNF-c-MOFs paper
Solvent	deionised water	50 mL	SI p.3 · Supplementary Experimental Section - Fabrication of CNF-c-MOFs paper

Complete recipeSource: SI

Route 7: Other

SI p.3 · Supplementary Experimental Section - Fabrication of CNF-c-MOFs paper

Metal precursorsNi-HITP c-MOF powder (15 mg)

Solventsdeionised water (50 mL) plus CNF suspension water

AdditivesCNF suspension (17 mL, 5 mg mL^-1)

Atmosphereambient

Temperature70 drying

Time20 min sonication; 12 h drying

Substrate orientationdirect mixed CNF/c-MOF paper control

Work-upsonicated 20 min, vacuum filtered, mould pressed between two metal plates

Activationdried at 70 C for 12 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Ni-HITP c-MOF powder	15 mg	SI p.3 · Supplementary Experimental Section - Fabrication of CNF-c-MOFs paper
Other	CNFs suspension	17 mL · 5 mg mL^-1	SI p.3 · Supplementary Experimental Section - Fabrication of CNF-c-MOFs paper
Solvent	deionised water	50 mL	SI p.3 · Supplementary Experimental Section - Fabrication of CNF-c-MOFs paper

Partial recipeSource: SI

Route 8: Other

SI p.2 · Supplementary Experimental Section - Pretreatment on Cladophora cellulose

Metal precursorsNi(NO3)2.6H2O, excess Ni2+ for ion exchange

Solventswater; 2 wt % NaOH solution

AdditivesTEMPO-mediated oxidation reagents described by previous study; NaOH pretreatment

Atmosphereroom atmosphere unless otherwise stated

Temperatureroom temperature for NaOH pretreatment

Time48 h NaOH pretreatment; 2 h Ni2+ ion exchange

Substrate orientationcellulose nanofiber suspension

Oxidant / reductantTEMPO-mediated oxidation; detailed TEMPO oxidation protocol referred to previous study

Work-upfiltered on 0.1 um PVDF membrane, washed with deionised water several times; ion-exchanged suspension filtrated and washed

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cladophora cellulose	Not specified	SI p.2 · Supplementary Experimental Section - Pretreatment on Cladophora cellulose
Base	NaOH solution	2 wt %	SI p.2 · Supplementary Experimental Section - Pretreatment on Cladophora cellulose
Oxidant	TEMPO-mediated oxidation reagents	described in previous study	SI p.2 · Supplementary Experimental Section - Pretreatment on Cladophora cellulose
Metal Source	Ni(NO3)2.6H2O	excessive Ni2+	SI p.2 · Supplementary Experimental Section - Pretreatment on Cladophora cellulose
Solvent	water	500 mL CNF suspension · 0.5 mg mL^-1 CNFs	SI p.2 · Supplementary Experimental Section - Pretreatment on Cladophora cellulose

Complete recipeSource: SI

Route 9: Other

SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder

Metal precursorsNi(OAc)2.4H2O (60 mg)

Linker precursorsHHTP (42 mg)

Solventswater; acetone for post-synthesis immersion

Temperature80; 70 drying

Time12 h reaction; 1 week acetone immersion; 12 h drying

Work-upblue dark powders immersed in acetone for 1 week, collected, and dried at 70 C for 12 h

Activationdried at 70 C for 12 h

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(OAc)2.4H2O	60 mg · in 10 mL water	SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder
Linker	HHTP	42 mg · in 10 mL water	SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder
Solvent	water	20 mL total	SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder
Solvent	acetone	immersion for 1 week	SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder

Complete recipeSource: SI

Route 10: Other

SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder

Metal precursorsNi(NO3)2.6H2O (66 mg)

Linker precursorsHITP.6HCl (100 mg)

Solventswater

Atmosphereair flow for first 2 h; then without air flow for additional 4 h

Temperature70

Time2 h under air flow plus 4 h without air flow; 12 h drying

Oxidant / reductantair flow during initial reaction period

Work-upblack precipitates collected and washed with deionised water three times

Activationdried at 70 C for 12 h

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Ni(NO3)2.6H2O	66 mg · in 10 mL water	SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder
Linker	HITP.6HCl	100 mg · in 25 mL water	SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder
Solvent	water	35 mL total stated as 10 mL + 25 mL	SI p.2 · Supplementary Experimental Section - Synthesis of c-MOFs powder

Complete recipeSource: SI

Route 11: Other

SI p.3 · Supplementary Experimental Section - Fabrication of pure c-MOF pellets · Figure S9

Metal precursorspure Ni-HHTP powder

Atmosphereambient

Work-uppressed in cylindrical hardened steel dry pressing die, 11 mm diameter, under 15 ton load

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	pure Ni-HHTP powder	Not specified	SI p.3 · Supplementary Experimental Section - Fabrication of pure c-MOF pellets · Figure S9

Complete recipeSource: SI

Route 12: Other

SI p.3 · Supplementary Experimental Section - Fabrication of pure c-MOF pellets · Figure S9

Metal precursorspure Ni-HITP powder

Atmosphereambient

Work-uppressed in cylindrical hardened steel dry pressing die, 11 mm diameter, under 15 ton load

Show 1 structured reagent record

Role	Reagent	Amount / concentration	Source
Other	pure Ni-HITP powder	Not specified	SI p.3 · Supplementary Experimental Section - Fabrication of pure c-MOF pellets · Figure S9